Abstract

The development of stable and efficient hydrogen evolution reaction (HER) catalysts is essential for the production of hydrogen as a clean energy resource. A combination of experiment and theory demonstrates that the normally inert basal planes of 2D layers of MoS 2 can be made highly catalytically active for the HER when alloyed with rhenium (Re). The presence of Re at the ≈50% level converts the material to a stable distorted tetragonal (DT) structure that shows enhanced HER activity as compared to most of the MoS 2-based catalysts reported in the literature. More importantly, this new alloy catalyst shows much better stability over time and cycling than lithiated 1T-MoS 2. Density functional theory calculations find that the role of Re is only to stabilize the DT structure, while catalysis occurs primarily in local Mo-rich DT configurations, where the HER catalytic activity is very close to that in Pt. The study provides a new strategy to improve the overall HER performance of MoS 2-based materials via chemical doping.

@article{osti_1490572,
title = {Rhenium-Doped and Stabilized MoS2 Atomic Layers with Basal-Plane Catalytic Activity},
author = {Yang, Shi-Ze and Gong, Yongji and Manchanda, Priyanka and Zhang, Yu-Yang and Ye, Gonglan and Chen, Shuangming and Song, Li and Pantelides, Sokrates T. and Ajayan, Pulickel M. and Chisholm, Matthew F. and Zhou, Wu},
abstractNote = {The development of stable and efficient hydrogen evolution reaction (HER) catalysts is essential for the production of hydrogen as a clean energy resource. A combination of experiment and theory demonstrates that the normally inert basal planes of 2D layers of MoS2 can be made highly catalytically active for the HER when alloyed with rhenium (Re). The presence of Re at the ≈50% level converts the material to a stable distorted tetragonal (DT) structure that shows enhanced HER activity as compared to most of the MoS2-based catalysts reported in the literature. More importantly, this new alloy catalyst shows much better stability over time and cycling than lithiated 1T-MoS2. Density functional theory calculations find that the role of Re is only to stabilize the DT structure, while catalysis occurs primarily in local Mo-rich DT configurations, where the HER catalytic activity is very close to that in Pt. The study provides a new strategy to improve the overall HER performance of MoS2-based materials via chemical doping.},
doi = {10.1002/adma.201803477},
journal = {Advanced Materials},
number = 51,
volume = 30,
place = {United States},
year = {Thu Oct 25 00:00:00 EDT 2018},
month = {Thu Oct 25 00:00:00 EDT 2018}
}

Significant interest has grown in the development of earth-abundant and efficient catalytic materials for hydrogen generation. Layered transition metal dichalcogenides present opportunities for efficient electrocatalytic systems. Here, we report the modification of 1D MoO x/MoS 2 core–shell nanostructures by lithium intercalation and the corresponding changes in morphology, structure, and mechanism of H 2 evolution. The 1D nanowires exhibit significant improvement in H 2 evolution properties after lithiation, reducing the hydrogen evolution reaction (HER) onset potential by ~50 mV and increasing the generated current density by ~600%. The high electrochemical activity in the nanowires results from disruption of MoS 2 layersmore » in the outer shell, leading to increased activity and concentration of defect sites. This is in contrast to the typical mechanism of improved catalysis following lithium exfoliation, i.e., crystal phase transformation. As a result, these structural changes are verified by a combination of Raman and X-ray photoelectron spectroscopy (XPS).« less

Monolayer molybdenum disulfide (MoS 2) has attracted tremendous attention due to its promising applications in high-performance field-effect transistors, phototransistors, spintronic devices, and nonlinear optics. The enhanced photoluminescence effect in monolayer MoS 2 was discovered and, as a strong tool, was employed for strain and defect analysis in MoS 2. Recently, large-size monolayer MoS 2 has been produced by chemical vapor deposition but has not yet been fully explored. Here we systematically characterize chemical vapor deposition grown MoS 2 by PL spectroscopy and mapping, and demonstrate non-uniform strain in single-crystalline monolayer MoS 2 and strain-induced band gap engineering. We also evaluatemore » the effective strain transferred from polymer substrates to MoS 2 by three-dimensional finite element analysis. In addition, our work demonstrates that PL mapping can be used as a non-contact approach for quick identification of grain boundaries in MoS 2.« less

2D layered MoS 2 has drawn intense attention for its applications in flexible electronic, optoelectronic, and spintronic devices. Most of the MoS 2 atomic layers grown by conventional chemical vapor deposition techniques are n-type due to the abundant sulfur vacancies. Facile production of MoS 2 atomic layers with p-type behavior, however, remains challenging. Here, a novel one-step growth has been developed to attain p-type MoS 2 layers in large scale by using Mo-containing sol–gel, including 1% tungsten (W). Atomic-resolution electron microscopy characterization reveals that small tungsten oxide clusters are commonly present on the as-grown MoS 2 film due to themore » incomplete reduction of W precursor at the reaction temperature. These omnipresent small tungsten oxide clusters contribute to the p-type behavior, as verified by density functional theory calculations, while preserving the crystallinity of the MoS 2 atomic layers. The Mo containing sol–gel precursor is compatible with the soft-lithography techniques, which enables patterned growth of p-type MoS 2 atomic layers into regular arrays with different shapes, holding great promise for highly integrated device applications. Lastly, an atomically thin p–n junction is fabricated by the as-prepared MoS 2, which shows strong rectifying behavior.« less

As a promising non-precious catalyst for the hydrogen evolution reaction, molybdenum disulphide (MoS 2) is known to contain active edge sites and an inert basal plane. Activating the MoS 2 basal plane could further enhance its HER activity but is not often a strategy for doing so. Herein, we report the first activation and optimization of the basal plane of monolayer 2H-MoS 2 for HER by introducing sulphur (S) vacancies and strain. Our theoretical and experimental results show that the S-vacancies are new catalytic sites in the basal plane, where gap states around the Fermi level allow hydrogen to bindmore » directly to exposed Mo atoms. The hydrogen adsorption free energy (ΔG H) can be further manipulated by straining the surface with S-vacancies, which fine-tunes the catalytic activity. Furthermore, proper combinations of S-vacancy and strain yield the optimal ΔG H = 0 eV, which allows us to achieve the highest intrinsic HER activity among molybdenum-sulphide-based catalysts.« less